JP2013159834A - Method for manufacturing resin-bonding aluminum-casting alloy member and resin-bonding aluminum-casting alloy member obtained by the method - Google Patents
Method for manufacturing resin-bonding aluminum-casting alloy member and resin-bonding aluminum-casting alloy member obtained by the method Download PDFInfo
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この発明は、アルミ鋳造合金からなる樹脂接合用のアルミ鋳造合金部材の製造方法及びこの方法で得られた樹脂接合用のアルミ鋳造合金部材に係り、特に限定するものではないが、自動車用部品、家電機器用部品、産業機器用部品等を始めとする多くの用途に好適な樹脂接合用アルミ鋳造合金部材の製造方法及びこの方法で得られた樹脂接合用のアルミ鋳造合金部材に関する。 The present invention relates to a method for producing an aluminum cast alloy member for resin bonding made of an aluminum cast alloy and an aluminum cast alloy member for resin bonding obtained by this method, although not particularly limited, parts for automobiles, The present invention relates to a method for producing a resin-bonded aluminum cast alloy member suitable for many applications including home appliance parts, industrial equipment parts, and the like, and an aluminum cast alloy member for resin bonding obtained by this method.
アルミニウム合金は、軽量で加工性に富むほか機械的性質にも優れ、しかも、優れた熱伝導性、導電性、耐食性等の特性を有することから、建築材料、家電機器用材料、車両・船舶用材料等の極めて多くの用途に供されており、特にアルミ鋳造合金部材については、アルミ押出合金部材とは異なり、単に熱伝導性や導電性等に優れているだけでなく、複雑な形状を有する部品であっても容易に作製することができることから、複雑な形状を有して熱伝導性や導電性等が求められる多くの用途に多用されており、そして、特に近年においては、かかる用途においても、その一部を熱的に及び／又は電気的に絶縁したい等のニーズから、部分的に断熱性や絶縁性に富む樹脂を接合することが求められている。 Aluminum alloys are lightweight and have excellent workability, as well as excellent mechanical properties, and excellent thermal conductivity, electrical conductivity, corrosion resistance, etc., so they are used for building materials, home appliance materials, vehicles and ships. Unlike aluminum extruded alloy members, especially aluminum cast alloy members are not only excellent in thermal conductivity and conductivity, but also have complicated shapes. Since parts can be easily manufactured, they are used in many applications that have complex shapes and require thermal conductivity, conductivity, etc. However, it is required to join a resin partially having a heat insulating property or an insulating property because of the need to thermally and / or electrically insulate a part thereof.
そして、このような用途に用いられ、部分的に樹脂を接合すること（部分的な樹脂化）が求められる場合において、これまではビス止めや接着剤等の手段が採用されていたが、これらの手段による部分的な樹脂化には、製造工程での工程数が増加するほか、重量増加の原因にもなり、これらビス止めや接着剤等の手段を必要としないアルミ−樹脂接合技術の開発が求められていた。 And when it is used for such applications and it is required to partially join the resin (partial resinization), means such as screws and adhesives have been used so far. Development of aluminum-resin bonding technology that increases the number of processes in the manufacturing process and causes weight increase, and does not require these means such as screws and adhesives. Was demanded.
そこで、本発明者らは、先に塩酸系エッチング処理によりアルミ合金部材の表面に微細な凹凸形状を付与し、この凹凸形状を利用して樹脂成形時にアルミ合金部材の表面に樹脂成形体を接合し、これによって過酷な環境下でも優れた密着性及び気密性を保持すると共に、優れた耐久性や耐熱性をも発揮するアルミ・樹脂射出一体成形品の製造方法を提供した（特許文献１）。しかしながら、アルミ鋳造合金は、通常その良好な鋳造性を確保するためにそのダイカスト鋳込み時に添加金属としてシリコン(Si)が添加され、Al-Si系アルミニウム合金として得られる。そして、このアルミ鋳造合金中に比較的多量に含まれるＳiがフッ酸以外の薬品にほとんど溶解しないことから、アルミ鋳造合金に上記のアルミ−樹脂接合技術をそのまま適用すると、アルミ鋳造合金のエッチング処理の際にその表面にＳiが溶け残って堆積し、この溶け残って堆積したＳiが、アルミ鋳造合金の表面上に樹脂成形体を接合した際に、これらアルミ鋳造合金と樹脂成形体との間の界面における密着性及び／又は気密性（以下、「アルミ樹脂接合性」という。）を損ね、このアルミ樹脂接合性に多大な悪影響を及ぼすという問題があった。 Therefore, the present inventors previously provided a fine uneven shape on the surface of the aluminum alloy member by hydrochloric acid etching treatment, and using this uneven shape, the resin molded body was joined to the surface of the aluminum alloy member during resin molding. As a result, a method for producing an aluminum / resin injection-integrated molded product that retains excellent adhesion and airtightness even in a harsh environment and also exhibits excellent durability and heat resistance is provided (Patent Document 1). . However, an aluminum cast alloy is usually obtained as an Al—Si based aluminum alloy by adding silicon (Si) as an additive metal at the time of die casting to ensure good castability. Since Si contained in a relatively large amount in this aluminum cast alloy hardly dissolves in chemicals other than hydrofluoric acid, if the above-mentioned aluminum-resin joining technique is applied to the aluminum cast alloy as it is, etching treatment of the aluminum cast alloy is performed. In this case, Si remains undissolved and accumulates on the surface, and when the undissolved Si accumulates on the surface of the aluminum cast alloy and joins the resin molded body, between the aluminum cast alloy and the resin molded body. There is a problem that the adhesion and / or airtightness (hereinafter referred to as “aluminum resin bondability”) at the interface is impaired and the aluminum resin bondability is greatly adversely affected.
本発明者らは、更にこのような問題を解決すべく検討し、Ｓi：５．０質量%以上１８質量%以下、Ｆe：１．３質量%以下、Ｃu：５．０質量%以下、Ｍg：１．５質量%以下、Ｎi：１．５質量%以下、及び残部がＡl及び不可避的不純物である成分組成のアルミ鋳造合金基材を鋳造するに際し、鋳造時の共晶Si凝固温度が７５５〜７８０℃である領域における冷却速度を０．１〜１００℃/秒とし、得られたアルミ鋳造合金基材について、必要によりその形状及びサイズを整えた後に、その表面を酸性エッチング液でエッチング処理し、このエッチング処理によって表面に凹状部を形成すると共にこの凹状部の内面に共晶Si結晶からなる所定の大きさの凸部を形成し、これによってアルミ樹脂接合性に優れたアルミ鋳造合金部材を製造する方法を提案した（特許文献２）。しかしながら、この方法においても、エッチング溶解量が最適値より僅かでも多くなると表層にＳiが堆積してアルミ樹脂接合性に悪影響を及ぼすという問題があるほか、エッチング溶解量の最適値が合金組成や表面組織に強く影響を受けるため、求められる合金組成や表面組織に応じてその都度エッチング処理の最適条件を設定する必要がある等の生産上の課題もある。 The present inventors further studied to solve such a problem. Si: 5.0% by mass or more and 18% by mass or less, Fe: 1.3% by mass or less, Cu: 5.0% by mass or less, Mg : 1.5% by mass or less, Ni: 1.5% by mass or less, and when casting an aluminum cast alloy base material having a composition in which the balance is Al and inevitable impurities, the eutectic Si solidification temperature during casting is 755. The cooling rate in the region of ˜780 ° C. is set to 0.1 to 100 ° C./second, and the obtained aluminum cast alloy base material is adjusted in shape and size as necessary, and then the surface is etched with an acidic etchant. Then, a concave portion is formed on the surface by this etching process, and a convex portion of a predetermined size made of eutectic Si crystal is formed on the inner surface of the concave portion, thereby making an aluminum cast alloy member excellent in aluminum resin bondability. Proposed method of manufacturing Patent Document 2). However, even in this method, if the etching dissolution amount is slightly larger than the optimum value, there is a problem that Si is deposited on the surface layer and adversely affects the aluminum resin bonding property, and the optimum etching dissolution amount depends on the alloy composition and the surface. Since it is strongly influenced by the structure, there are also production problems such as the need to set the optimum conditions for the etching process each time according to the required alloy composition and surface structure.
そこで、本発明者らは、ダイカスト鋳込みにより調製されたアルミニウム合金からなるアルミ鋳造合金基材の表面に簡便な方法で凹凸形状を付与し、優れたアルミ樹脂接合性を有するアルミ鋳造合金部材を容易に製造することができる方法について鋭意検討した結果、意外なことには、Ｓi原子及びＭg原子をそれぞれ所定の範囲内で含むアルミ鋳造合金基材を調製し、このアルミ鋳造合金基材の表面に晶出したMg2Si晶出物を特定の酸性エッチング液で所定の条件下にエッチング処理することにより、アルミ樹脂接合性に優れたアルミ鋳造合金部材を容易に製造できることを見い出し、本発明を完成した。 Therefore, the present inventors easily provide an aluminum cast alloy member having excellent aluminum resin bonding properties by imparting an uneven shape to the surface of an aluminum cast alloy base material made of an aluminum alloy prepared by die casting by a simple method. As a result of intensive investigations on methods that can be manufactured, it is surprising that an aluminum cast alloy base material containing Si atoms and Mg atoms within a predetermined range is prepared, and the surface of the aluminum cast alloy base material is prepared. We found that by casting the crystallized Mg 2 Si crystallized material with a specific acidic etchant under specified conditions, it was possible to easily produce an aluminum cast alloy member with excellent aluminum resin bonding properties, and the present invention was completed. did.
従って、本発明の目的は、アルミ樹脂接合性に優れたアルミ鋳造合金部材を簡便な方法で容易に製造することができる樹脂接合用アルミ鋳造合金部材の製造方法を提供することにあり、また、この方法で得られた樹脂接合用アルミ鋳造合金部材を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing an aluminum cast alloy member for resin bonding, which can easily produce an aluminum cast alloy member excellent in aluminum resin bondability by a simple method. An object of the present invention is to provide an aluminum cast alloy member for resin bonding obtained by this method.
すなわち、本発明は、ダイカスト鋳込みによりＳi：０．９〜１８質量%及びＭg：１．０〜１０．０質量%の範囲で含有するアルミ鋳造合金からなるアルミ鋳造合金基材を調製し、次いで硫酸及び／又は硝酸の水溶液からなる酸性エッチング液を用い、上記アルミ鋳造合金基材を処理温度３０〜８０℃及び処理時間５〜１５分の条件でエッチング処理してこのアルミ鋳造合金基材表面のMg2Si晶出物を溶解し、前記アルミ鋳造合金基材の表面に樹脂接合性に優れた微細な凹凸形状を付与することを特徴とする樹脂接合用アルミ鋳造合金部材の製造方法である。 That is, the present invention prepares an aluminum cast alloy base material made of an aluminum cast alloy containing Si: 0.9 to 18% by mass and Mg: 1.0 to 10.0% by mass by die casting, Using an acidic etching solution composed of an aqueous solution of sulfuric acid and / or nitric acid, the aluminum cast alloy base material was etched at a treatment temperature of 30 to 80 ° C. and a treatment time of 5 to 15 minutes. A method for producing an aluminum cast alloy member for resin bonding, comprising melting an Mg 2 Si crystallized product and imparting a fine uneven shape excellent in resin bondability to the surface of the aluminum cast alloy base material.
本発明において、ダイカスト鋳込みにより調製されるアルミ鋳造合金基材は、そのアルミ鋳造合金がマトリクス金属のアルミニウム（Al）以外に、少なくともＳi原子を０．９質量%以上１８質量%以下、好ましくは３質量%以上１５質量%以下の範囲で、また、Ｍg原子を１．０質量%以上１０．０質量%以下、好ましくは１．５質量%以上９質量%以下の範囲で含むことが必要であり、Ｓi原子含有量が０．９質量%より低いとダイカスト鋳込み時の湯流れが悪くなり、反対に１８質量%より高くなると調製されたアルミ鋳造合金の靭性が低下して好ましくなく、また、Ｍg原子含有量が１．０質量%より低いと十分なＭg2Ｓiが得られないという問題があり、反対に１０．０質量%より高くなると鋳造性が著しく低下するという問題が生じる。 In the present invention, the aluminum cast alloy base material prepared by die casting is 0.9 mass% or more and 18 mass% or less, preferably 3 at least Si atoms in addition to the matrix metal aluminum (Al). It is necessary to contain Mg atoms in the range of not less than 15% by mass and not more than 15% by mass, and in the range of not less than 1.0% by mass and not more than 10.0% by mass, preferably not less than 1.5% by mass and not more than 9% by mass. If the Si atom content is lower than 0.9% by mass, the molten metal flow at the time of die casting becomes worse. On the other hand, if the Si atom content exceeds 18% by mass, the toughness of the prepared aluminum casting alloy decreases, which is not preferable. When the atomic content is lower than 1.0% by mass, there is a problem that sufficient Mg 2 Si cannot be obtained. On the other hand, when the atomic content is higher than 10.0% by mass, there arises a problem that castability is remarkably lowered.
また、このアルミ鋳造合金基材を構成するアルミ鋳造合金については、通常、鋳造時の金型への焼き付け防止に必要な元素としてＦe及びＭnが存在するが、Ｆeについては、特定の酸性エッチング浴では溶解しないAl-Fe-Si系金属間化合物を形成してＭg2Ｓiを形成するのに必要なＳiを消費させる等、アルミ樹脂接合性に悪影響を与えるので、０．０１質量%以上０．８質量%以下、好ましくは０．１質量%以上０．７質量%以下の範囲で添加するのがよく、また、Ｍnについては、特定の酸性エッチング浴では溶解しないＡl-Ｍn系やＡl-Ｍn-Ｓi系の金属間化合物を形成し、前者はエッチング時に凹部が形成されない場所を増やし、また、後者はＭg2Ｓiを形成するのに必要なＳiを消費させる等のアルミ樹脂接合性に悪影響を与えることから、０．０１質量%以上０．９質量%以下、好ましくは０．１質量%以上０．８質量%以下の範囲で添加するのがよい。 Moreover, about the aluminum cast alloy which comprises this aluminum cast alloy base material, although Fe and Mn exist as an element normally required for the baking prevention to the metal mold | die at the time of casting, about a specific acidic etching bath In this case, the Al-Fe-Si intermetallic compound which does not dissolve is formed, and the Si resin necessary for forming Mg 2 Si is consumed. 8% by mass or less, preferably 0.1% by mass or more and 0.7% by mass or less. Mn is not dissolved in a specific acidic etching bath, and Al-Mn or Al-Mn. -Si-based intermetallic compounds are formed, the former increases the number of places where no recesses are formed during etching, and the latter adversely affects aluminum resin bonding properties, such as consuming Si required to form Mg 2 Si. 0.01 quality from giving % To 0.9 wt% or less, and it is preferably added in the range of less than 0.8 mass% 0.1 mass% or more.
更に、このアルミ鋳造合金については、アルミ鋳造合金基材の材料強度を向上させるために必要な元素のＣuを添加してもよく、Ｃuを添加する場合には、特定の酸性エッチング浴では溶解しないＡl-Ｃu系やＡl-Ｃu-Ｍg系の金属間化合物を形成し、前者はエッチング時に凹部が形成されない場所を増やし、また、後者はＭg2Ｓiを形成するのに必要なＭgを消費させる等、アルミ樹脂接合性に悪影響を与えるので、通常０．０１質量%以上１．０質量%以下、好ましくは０．０２質量%以上０．８質量%以下の範囲で添加するのがよい。なお、このアルミ鋳造合金には、不可避不純物としてＮiが混入するが、このＮiは特定の酸性エッチング浴では溶解しないＡl-Ｎi系やＡl-Ｆe-Ｎi系の金属間化合物を形成し、エッチング時に凹部が形成されない場所を増やし、アルミ樹脂接合性に悪影響を与えるので、好ましくは０．１質量%以下に抑えるのが望ましい。 Further, for this aluminum cast alloy, Cu, an element necessary for improving the material strength of the aluminum cast alloy base material, may be added. When Cu is added, it does not dissolve in a specific acidic etching bath. Forms Al-Cu-based and Al-Cu-Mg-based intermetallic compounds, the former increases the number of places where recesses are not formed during etching, the latter consumes Mg necessary to form Mg 2 Si, etc. Since it adversely affects the aluminum resin bondability, it is usually added in the range of 0.01 to 1.0% by mass, preferably 0.02 to 0.8% by mass. In this aluminum casting alloy, Ni is mixed as an inevitable impurity, but this Ni forms an Al-Ni-based or Al-Fe-Ni-based intermetallic compound that does not dissolve in a specific acidic etching bath. Since the number of places where the concave portions are not formed is increased and the aluminum resin bonding property is adversely affected, it is preferable to keep the amount to 0.1% by mass or less.
ここで、本発明のアルミ鋳造合金基材については、後のエッチング処理によって得られるアルミ鋳造合金部材の表面に所望のアルミ樹脂接合性を付与するために、好ましくは表面におけるMg2Si晶出物の面積比率〔すなわち、エネルギー分散型Ｘ線分析装置（堀場製作所製EMAX-7000）の反射電子像観察（図１）とマッピング分析によりSi元素及びAl元素の分析を行い、その後、Ｓｉ元素とＡｌ元素を重ね合わせ、図２のように画像処理して求められるMg2Si晶出物の測定視野０．１mm角における面積比率〕が５%以上６０%以下、好ましくは１５%以上５０%以下であるのがよい。このMg2Si晶出物の面積比率が５%より低いとエッチングによる凹凸形状の形成に不利に働くため、樹脂接合性に悪影響を与えるという問題があり、反対に、６０%より高くなると形成される凹凸形状のサイズが大きくなり過ぎて樹脂接合性に悪影響を与えるという問題が生じる虞がある。 Here, with respect to the aluminum cast alloy base material of the present invention, in order to impart desired aluminum resin bondability to the surface of the aluminum cast alloy member obtained by the subsequent etching treatment, preferably Mg 2 Si crystallized material on the surface Area ratio [that is, analysis of Si element and Al element by reflection electron image observation (Fig. 1) and mapping analysis of energy dispersive X-ray analyzer (EMAX-7000 manufactured by Horiba, Ltd.), and then Si element and Al The area ratio of the Mg 2 Si crystallized substance obtained by superimposing the elements and performing image processing as shown in FIG. 2 at a measurement visual field of 0.1 mm square is 5% or more and 60% or less, preferably 15% or more and 50% or less. There should be. If the area ratio of this Mg 2 Si crystallized substance is lower than 5%, it will adversely affect the formation of concave and convex shapes by etching, so that there is a problem of adversely affecting the resin bondability. There is a concern that the size of the uneven shape may become too large and adversely affect the resin bondability.
そこで、このアルミ鋳造合金基材の表面におけるMg2Si晶出物の面積率が上記の５%に達していない場合には、次のエッチング処理に先駆けて、アルミ鋳造合金基材に時効処理を施し、好ましくは溶体化処理を施した後に時効処理を施し、アルミ鋳造合金基材表面のMg2Si晶出物面積率を上記の範囲内に調整するのがよい。 Therefore, when the area ratio of Mg 2 Si crystallized material on the surface of the aluminum cast alloy base material does not reach the above 5%, the aluminum cast alloy base material is subjected to an aging treatment prior to the next etching process. It is preferable to apply an aging treatment after the solution treatment, and to adjust the Mg 2 Si crystallized area ratio of the aluminum cast alloy substrate surface within the above range.
この目的で行われるアルミ鋳造合金基材の時効処理については、処理温度が１８０℃以上４００℃以下、好ましくは２００℃以上３８０℃以下であって、処理時間が０．５時間以上２０時間以下、好ましくは１時間以上１５時間以下の処理条件であるのがよく、また、この時効処理の前に溶体化処理を施す場合には、この溶体化処理の処理条件として、処理温度が４８０℃以上６００℃以下、好ましくは５００℃以上５８０℃以下であって、処理時間が０．５時間以上２０時間以下、好ましくは１時間以上１５時間以下であるのがよい。上記時効処理の処理条件において、処理温度が１８０℃より低いとＭg2Ｓiが十分に析出しないという問題があり、反対に、４００℃より高くなるとＭg2Ｓiの析出サイズが粗大になりすぎて分散性が低下する虞があり、また、処理時間が０．５時間より少ないとＭg2Ｓiが十分に析出しないという問題があり、反対に、１５時間より長くなるとＭg2Ｓi析出サイズが粗大になりすぎて分散性が低下する虞がある。 For the aging treatment of the aluminum cast alloy substrate performed for this purpose, the treatment temperature is 180 ° C. or more and 400 ° C. or less, preferably 200 ° C. or more and 380 ° C. or less, and the treatment time is 0.5 hours or more and 20 hours or less, The treatment conditions are preferably 1 hour or more and 15 hours or less, and when the solution treatment is performed before this aging treatment, the treatment temperature is 480 ° C. or more and 600 ° C. as the treatment conditions for the solution treatment. The processing time is 0.5 to 20 hours, preferably 1 to 15 hours, preferably 500 ° C. or less, preferably 500 to 580 ° C. Under the above aging treatment conditions, if the treatment temperature is lower than 180 ° C., there is a problem that Mg 2 Si does not sufficiently precipitate. Conversely, if the treatment temperature is higher than 400 ° C., the Mg 2 Si precipitation size becomes too coarse and dispersed. When the treatment time is less than 0.5 hours, Mg 2 Si is not sufficiently precipitated. Conversely, when the treatment time is longer than 15 hours, the Mg 2 Si precipitation size becomes coarse. Too much dispersibility may be deteriorated.
このようにして調製されたアルミ鋳造合金基材については、次に、硫酸及び／又は硝酸の水溶液からなる酸性エッチング液を用いてエッチング処理を行い、このアルミ鋳造合金基材の表面に存在するMg2Si晶出物を溶解し、アルミ鋳造合金基材の表面に所望の凹凸形状を形成せしめる。 The aluminum cast alloy base material thus prepared is then subjected to an etching treatment using an acidic etchant composed of an aqueous solution of sulfuric acid and / or nitric acid, and Mg present on the surface of the aluminum cast alloy base material. 2 Dissolve the Si crystallized product to form the desired uneven shape on the surface of the aluminum cast alloy substrate.
ここで、酸性エッチング液として用いる硫酸及び／又は硝酸の水溶液については、硫酸水溶液の場合にはその酸濃度が１重量%以上６０重量%以下、好ましくは５重量%以上５０重量%以下であるのがよく、また、硝酸水溶液の場合にはその酸濃度が５重量%以上６０重量%以下、好ましくは１０重量%以上５０重量%以下であるのがよく、更に、硫酸・硝酸混合水溶液の場合には酸濃度が５重量%以上５０重量%以下である硫酸水溶液中に酸濃度が５重量%以上３０重量%以下である硝酸水溶液を添加するのがよい。酸性エッチング液の酸濃度が上記範囲より低いと反応が十分に進まず溶解量が不十分になるという問題が生じる虞があり、反対に、上記範囲より高くなると反応速度が速くなり過ぎて溶解量の制御が困難になる。なお、上記の酸性エッチング液については、溶解量を制御する等の目的のため、必要によりクロム酸、リン酸、酢酸、シュウ酸、アスコルビン酸、安息香酸、酪酸、クエン酸、ぎ酸、乳酸、イソブチル酸、リンゴ酸、プロピオン酸、酒石酸等の硫酸及び硝酸以外の酸を添加してもよい。 Here, the sulfuric acid and / or nitric acid aqueous solution used as the acidic etching solution has an acid concentration of 1% by weight to 60% by weight, preferably 5% by weight to 50% by weight in the case of sulfuric acid aqueous solution. In the case of an aqueous nitric acid solution, the acid concentration should be 5 to 60% by weight, preferably 10 to 50% by weight. It is preferable to add a nitric acid aqueous solution having an acid concentration of 5% by weight to 30% by weight to a sulfuric acid aqueous solution having an acid concentration of 5% by weight to 50% by weight. If the acid concentration of the acidic etching solution is lower than the above range, there is a possibility that the reaction does not proceed sufficiently and the amount of dissolution becomes insufficient. On the other hand, if the acid concentration is higher than the above range, the reaction rate becomes too fast and the amount of dissolution is high. It becomes difficult to control. For the above acidic etching solution, for the purpose of controlling the amount of dissolution, chromic acid, phosphoric acid, acetic acid, oxalic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, formic acid, lactic acid, Acids other than sulfuric acid and nitric acid such as isobutyric acid, malic acid, propionic acid, and tartaric acid may be added.
また、上記の酸性エッチング液を用いたエッチング処理の処理条件については、処理温度が通常２０℃以上９０℃以下、好ましくは３０℃以上８０℃以下であって、処理時間が通常１分以上２０分以下、好ましくは５分以上１５分以下であるのがよい。このエッチング処理の処理条件における処理温度が２０℃より低いと反応が十分に進まず溶解量が不十分になる虞があり、反対に、９０℃より高くなると反応速度が速くなり過ぎて溶解量の制御が困難になる。同様に、エッチング処理の処理時間が１分より短いと反応が十分に進まず溶解量が不十分になる虞があり、反対に、２０分より長くなると生産効率が低下して量産性が悪くなる。 In addition, with respect to the processing conditions of the etching process using the above acidic etching solution, the processing temperature is usually 20 ° C. or higher and 90 ° C. or lower, preferably 30 ° C. or higher and 80 ° C. or lower, and the processing time is usually 1 minute or longer and 20 minutes or shorter. Hereinafter, it is preferably 5 minutes or more and 15 minutes or less. If the processing temperature under the processing conditions of this etching process is lower than 20 ° C., the reaction may not proceed sufficiently and the amount of dissolution may be insufficient. On the other hand, if the processing temperature is higher than 90 ° C., the reaction rate becomes too high and Control becomes difficult. Similarly, if the processing time of the etching process is shorter than 1 minute, the reaction may not proceed sufficiently and the amount of dissolution may be insufficient. On the other hand, if the processing time is longer than 20 minutes, the production efficiency decreases and the mass productivity deteriorates. .
本発明において、以上のようにして得られたアルミ鋳造合金基材の表面にコンタミ等が残渣している場合には、脱脂や表面調整、表面付着物・汚染物等の除去を目的に、このアルミ鋳造合金基材のエッチング処理に先駆けて、酸水溶液に浸漬した後にアルカリ水溶液に浸漬する前処理を行うのがよい。この目的で使用される酸水溶液としては、例えば、市販の酸性脱脂剤で調製したもの、硫酸、硝酸、フッ酸、リン酸等の鉱酸や酢酸、クエン酸等の有機酸や、これらの酸を混合して得られた混合酸等の酸試薬を用いて調製したもの等の酸の１〜５０重量%水溶液が用いるのがよく、また、アルカリ水溶液としては、例えば、市販のアルカリ性脱脂剤により調製したもの、苛性ソーダ等のアルカリ試薬により調製したもの、又はこれらのものを混合して調製したもの等のアルカリの１〜５０重量%水溶液が用いるのがよく、更に、浸漬時間については、酸水溶液及びアルカリ水溶液のいずれの場合も０．５〜１０分間程度であるのがよい。 In the present invention, when contaminants and the like remain on the surface of the aluminum cast alloy base material obtained as described above, for the purpose of degreasing and surface adjustment, removal of surface deposits and contaminants, etc. Prior to the etching treatment of the aluminum cast alloy base material, it is preferable to perform a pretreatment of immersing in an aqueous alkali solution after immersing in an aqueous acid solution. Examples of the acid aqueous solution used for this purpose include those prepared with commercially available acidic degreasing agents, mineral acids such as sulfuric acid, nitric acid, hydrofluoric acid, and phosphoric acid, organic acids such as acetic acid and citric acid, and these acids. It is preferable to use an aqueous solution of 1 to 50% by weight of an acid such as one prepared by using an acid reagent such as a mixed acid obtained by mixing, and as an alkaline aqueous solution, for example, by a commercially available alkaline degreasing agent It is preferable to use a 1 to 50% by weight aqueous solution of an alkali such as a prepared one, one prepared with an alkaline reagent such as caustic soda, or one prepared by mixing these, and the immersion time is preferably an acid aqueous solution. In both cases, the alkaline aqueous solution should be about 0.5 to 10 minutes.
本発明により得られたアルミ鋳造合金部材は、上記のエッチング処理によって溶解されたMg2Si晶出物の跡が凹状部となってこのアルミ鋳造合金部材の表面に凹凸形状を形成し、この凹凸形状により樹脂成形体との間に優れたアルミ樹脂接合性を発現する。そして、本発明のアルミ鋳造合金部材において、アルミ鋳造合金部材の表面に観察される凹状部の面積比率〔すなわち、操作型電子顕微鏡（日立製FE-SEM、S-4500形）を用いてＳＥＭ像（図３）を観察し、その結果を図４のように画像処理して求められる測定視野０．１ｍｍ角における凹状部の面積比率〕が２０%以上９０%以下、好ましくは３５%以上８０%以下であるのがよい。アルミ鋳造合金部材の表面における凹状部の面積率が２０%より低いと凹部に入り込む樹脂量が不十分になり、樹脂接合性に悪影響を及ぼすという問題が生じる虞があり、反対に、９０%より高くなると凹部に入り込んだ樹脂を支えるためのアルミ部が極端に少なくなり、結果として樹脂接合性に悪影響を及ぼすという問題が生じる虞が生じる。 In the aluminum cast alloy member obtained by the present invention, the trace of the Mg 2 Si crystallized material dissolved by the above etching process becomes a concave portion to form an uneven shape on the surface of the aluminum cast alloy member. Excellent aluminum resin bondability between the molded resin and its shape. Then, in the aluminum cast alloy member of the present invention, the area ratio of the concave portions observed on the surface of the aluminum cast alloy member [ie, SEM image using an operation electron microscope (Hitachi FE-SEM, S-4500 type) (FIG. 3) and the area ratio of the concave portion in the measurement visual field 0.1 mm square obtained by image processing as shown in FIG. 4 is 20% or more and 90% or less, preferably 35% or more and 80%. It should be: If the area ratio of the concave portion on the surface of the aluminum cast alloy member is lower than 20%, the amount of resin entering the concave portion may be insufficient, which may cause a problem of adversely affecting the resin bondability. When the height is increased, the aluminum portion for supporting the resin that has entered the recess is extremely reduced, and as a result, there is a possibility that a problem of adversely affecting the resin bondability may occur.
本発明の方法により得られたアルミ鋳造合金部材は、その表面に形成された微細な凹凸形状により、例えばこのアルミ鋳造合金部材を射出成形用金型内にセットし、この金型内に溶融した所定の熱可塑性樹脂を射出して固化させる、いわゆるアルミ鋳造合金部材を用いた熱可塑性樹脂の射出一体成形により、アルミ鋳造合金部材の必要な部分に樹脂成形体を接合してアルミ−樹脂複合体を製造した際に、優れたアルミ樹脂接合性を発揮する。 The aluminum cast alloy member obtained by the method of the present invention has, for example, the aluminum cast alloy member set in an injection mold and melted in the mold due to the fine uneven shape formed on the surface thereof. A resin molded body is joined to a required portion of an aluminum cast alloy member by injection molding of a thermoplastic resin using a so-called aluminum cast alloy member, in which a predetermined thermoplastic resin is injected and solidified, and an aluminum-resin composite. When it is manufactured, it exhibits excellent aluminum resin bondability.
ここで、本発明のアルミ鋳造合金部材を用いたアルミ−樹脂複合体を製造する際に使用される熱可塑性樹脂としては、各種の熱可塑性樹脂を単独で用いることができるが、本発明のアルミ鋳造合金部材を用いて製造されるアルミ−樹脂複合体に求められる物性、用途、使用環境等を考慮すると、熱可塑性樹脂としては、好ましくは、例えばポリプロピレン樹脂、ポリエチレン樹脂、アクリロニトリル・ブタジエン・スチレン共重合体（ABS）、ポリカーボネート樹脂（PC）、ポリアミド樹脂（PA）、ポリフェニレンスルフィド（PPS）等のポリアリーレンサルファイド樹脂、ポリアセタール樹脂、液晶性樹脂、ポリエチレンテレフタレート（PET）やポリブチレンテレフタレート（PBT）等のポリエステル系樹脂、ポリオキシメチレン樹脂、ポリイミド樹脂、シンジオタクティックポリスチレン樹脂等やこれらの熱可塑性樹脂の２種以上の混合物が挙げられ、また、アルミ形状体と樹脂成形体との間の密着性、機械的強度、耐熱性、寸法安定性（耐変形、反り等）、電気的性質等の性能をより改善するために、より好ましくは、これらの熱可塑性樹脂に繊維状、粉粒状、板状等の充填剤や、各種のエラストマー成分を添加するのがよい。 Here, as the thermoplastic resin used when producing the aluminum-resin composite using the aluminum cast alloy member of the present invention, various thermoplastic resins can be used alone, but the aluminum of the present invention is used. Considering the physical properties required for an aluminum-resin composite manufactured using a cast alloy member, usage, usage environment, etc., the thermoplastic resin is preferably a polypropylene resin, polyethylene resin, acrylonitrile / butadiene / styrene, for example. Polymers (ABS), polycarbonate resins (PC), polyamide resins (PA), polyarylene sulfide resins such as polyphenylene sulfide (PPS), polyacetal resins, liquid crystalline resins, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) Polyester resin, polyoxymethylene resin, polyimide Examples include resins, syndiotactic polystyrene resins, and mixtures of two or more of these thermoplastic resins. Adhesion between aluminum shaped body and resin molded body, mechanical strength, heat resistance, dimensional stability In order to further improve the performance such as (deformation resistance, warpage, etc.) and electrical properties, more preferably, these thermoplastic resins are filled with fillers such as fibrous, granular, plate-like, and various elastomer components. It is good to add.
また、熱可塑性樹脂に添加される充填剤としては、ガラス繊維、カーボン繊維、金属繊維、アスベスト繊維、硼素繊維等の無機質繊維充填剤や、ポリアミド、フッ素樹脂、アクリル樹脂等の高融点有機質繊維充填剤や、石英粉末、ガラスビーズ、ガラス粉、炭酸カルシウムを始めとする無機粉体類等の粉状充填剤や、ガラスフレーク、タルクやマイカ等の珪酸塩類等の板状充填剤等が例示され、熱可塑性樹脂１００重量部に対して２５０重量部以下、好ましくは２０重量部以上２２０重量部以下、より好ましくは３０重量部以上１００重量部以下の範囲で添加される。この充填剤の添加量が２５０重量部を超えると、流動性が低下しアルミ形状体の凹部へ進入し難くなり良好な密着強度を得られなかったり、機械的特性の低下を招くという問題が生じる。 Fillers added to thermoplastic resins include inorganic fiber fillers such as glass fibers, carbon fibers, metal fibers, asbestos fibers and boron fibers, and high melting point organic fibers such as polyamides, fluororesins and acrylic resins. And powder fillers such as silica powder, glass beads, glass powder, inorganic powders such as calcium carbonate, and plate fillers such as glass flakes, silicates such as talc and mica, etc. In addition, it is added in an amount of 250 parts by weight or less, preferably 20 parts by weight or more and 220 parts by weight or less, more preferably 30 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. When the added amount of the filler exceeds 250 parts by weight, there is a problem that the fluidity is lowered and it is difficult to enter the concave portion of the aluminum shaped body, and good adhesion strength cannot be obtained or the mechanical properties are deteriorated. .
また、熱可塑性樹脂に添加されるエラストマー成分としては、ウレタン系、コアシェル型、オレフィン系、ポリエステル系、アミド系、スチレン系等のエラストマーが例示され、射出成形時の熱可塑性樹脂の溶融温度等を考慮して選択され、また、熱可塑性樹脂１００重量部に対して３０重量部以下、好ましくは３〜２５重量部の範囲で使用される。このエラストマー成分の添加量が３０重量部を超えると、更なる密着強度向上効果が見られず機械的特性の低下等の問題が生じる。このエラストマー成分の配合効果は、熱可塑性樹脂としてポリエステル系樹脂を用いた場合に特に顕著に現れる。 Examples of the elastomer component added to the thermoplastic resin include urethane type, core shell type, olefin type, polyester type, amide type, styrene type elastomers, etc. In addition, it is selected in consideration of 30 parts by weight or less, preferably 3 to 25 parts by weight based on 100 parts by weight of the thermoplastic resin. When the added amount of the elastomer component exceeds 30 parts by weight, a further effect of improving the adhesion strength is not seen, and problems such as a decrease in mechanical properties occur. This blending effect of the elastomer component is particularly prominent when a polyester resin is used as the thermoplastic resin.
更に、本発明のアルミ−樹脂複合体を製造するための熱可塑性樹脂には、一般に熱可塑性樹脂に添加される公知の添加剤、すなわち難燃剤、染料や顔料等の着色剤、酸化防止剤や紫外線吸収剤等の安定剤、可塑剤、潤滑剤、滑剤、離型剤、結晶化促進剤、結晶核剤等を、要求される性能に応じて適宜添加することができる。 Further, the thermoplastic resin for producing the aluminum-resin composite of the present invention includes known additives generally added to thermoplastic resins, that is, flame retardants, colorants such as dyes and pigments, antioxidants, Stabilizers such as ultraviolet absorbers, plasticizers, lubricants, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, and the like can be appropriately added according to the required performance.
本発明において、アルミ鋳造合金部材を射出成形用金型内にセットして行う熱可塑性樹脂の射出成形については、用いられる熱可塑性樹脂に求められる成形条件を採用し得るものであるが、射出成形時に溶融した熱可塑性樹脂がアルミ鋳造合金部材の凹状部内に確実に進入して固化することが重要であり、金型温度やシリンダー温度を熱可塑性樹脂の種類や物性、更には成形サイクルの許す範囲で比較的高めに設定するのが好ましく、特に金型温度については、下限温度を９０℃以上、好ましくは１３０℃以上にする必要があるが、上限は、使用する熱可塑性樹脂の種類に応じて、１００℃から当該熱可塑性樹脂の融点又は軟化点（エラストマー成分が添加される場合にはどちらか高い方の融点又は軟化点）より２０℃程度低い温度までの範囲であるのがよい。また、下限金型温度は、熱可塑性樹脂の融点から１４０℃以上低くならないように設定するのが好ましい。 In the present invention, for the injection molding of the thermoplastic resin performed by setting the aluminum cast alloy member in the injection mold, the molding conditions required for the thermoplastic resin used can be adopted. It is important that the molten thermoplastic resin sometimes penetrates into the concave part of the aluminum cast alloy member and solidifies, and the mold temperature and cylinder temperature are within the range allowed by the type and physical properties of the thermoplastic resin and the molding cycle. It is preferable that the lower limit temperature be 90 ° C. or higher, preferably 130 ° C. or higher, but the upper limit depends on the type of thermoplastic resin used. The range from 100 ° C. to a temperature about 20 ° C. lower than the melting point or softening point of the thermoplastic resin (the higher melting point or softening point when an elastomer component is added). In which the good is. Further, the lower limit mold temperature is preferably set so as not to be lowered by 140 ° C. or more from the melting point of the thermoplastic resin.
なお、本発明のアルミ鋳造合金部材を用いて行われるアルミ−樹脂複合体の製造方法については、上記の熱可塑性樹脂の射出一体成形法に限らず、熱圧着法を採用してもよい。すなわち、先ず、使用する熱可塑性樹脂の溶融温度に応じてアルミ鋳造合金部材を９０〜３００℃程度の温度に加熱し、その表面に熱可塑性樹脂性の樹脂成形体を加圧下に押し当て、この樹脂成形体の表面の一部を溶融させてアルミ鋳造合金部材表面の凹状部内に侵入させ、更に加圧下に冷却することにより所望のアルミ−樹脂複合体を製造する。 In addition, about the manufacturing method of the aluminum resin composite performed using the aluminum casting alloy member of this invention, you may employ | adopt not only the said injection integral molding method of a thermoplastic resin but a thermocompression bonding method. That is, first, the aluminum casting alloy member is heated to a temperature of about 90 to 300 ° C. according to the melting temperature of the thermoplastic resin to be used, and a thermoplastic resin-based molded body is pressed under pressure to the surface, A desired aluminum-resin composite is manufactured by melting a part of the surface of the resin molded body and penetrating into the concave portion of the surface of the aluminum cast alloy member and further cooling under pressure.
本発明方法によれば、ダイカスト鋳込みにより調製されたアルミ鋳造合金基材の表面に簡便な方法で凹凸形状を形成し、アルミ樹脂接合性に優れたアルミ鋳造合金部材を容易に製造することができる。しかも、添加金属としてＳi原子に加えてＭg原子が添加されるので、製造されるアルミ鋳造合金部材の材料強度がより一層向上し、より広い用途のアルミ−樹脂複合体を製造するための材料として利用することができる。 According to the method of the present invention, a concavo-convex shape can be formed by a simple method on the surface of an aluminum cast alloy base material prepared by die casting, and an aluminum cast alloy member excellent in aluminum resin bondability can be easily manufactured. . Moreover, since Mg atoms are added in addition to Si atoms as the additive metal, the material strength of the aluminum cast alloy member to be produced is further improved, and as a material for producing an aluminum-resin composite for wider use. Can be used.
以下、本発明の実施例及び比較例に基づいて、本発明の実施の形態を具体的に説明する。 Embodiments of the present invention will be specifically described below based on examples and comparative examples of the present invention.
〔実施例１〕
１．アルミ鋳造合金基材の調製
Ｓi：３．３質量%、Ｆe：０．４質量%、Ｃu：０．０２質量%、Ｍn：０．４質量%、Ｍg：６．０質量%、Ｎi：０．０２質量%を含むアルミ合金溶湯を、１８０mm×１５０mm×３mmのサイズにダイカスト鋳込みを行った。なお、この際の設定条件は、金型温度；１７０℃、溶湯温度；７２０℃、射出速度；１．７m/s、製品充填時間；１０ms、製品内平均流速；１１m/sである。なお、鋳造時の冷却速度は４０℃/秒である。得られたアルミ鋳造合金基材から４０mm×４０mm×３mmの大きさのアルミ基材試験片を切り出した。
[Example 1]
1. Preparation of Aluminum Cast Alloy Base Material Si: 3.3% by mass, Fe: 0.4% by mass, Cu: 0.02% by mass, Mn: 0.4% by mass, Mg: 6.0% by mass, Ni: 0 A molten aluminum alloy containing 0.02% by mass was die-cast into a size of 180 mm × 150 mm × 3 mm. In this case, the setting conditions are: mold temperature: 170 ° C., molten metal temperature: 720 ° C., injection speed: 1.7 m / s, product filling time: 10 ms, in-product average flow velocity: 11 m / s. The cooling rate during casting is 40 ° C./second. An aluminum base specimen having a size of 40 mm × 40 mm × 3 mm was cut out from the obtained aluminum cast alloy base.
２．アルミ鋳造合金基材の表面観察
得られたアルミ基材試験片の表面について、エネルギー分散型Ｘ線分析装置（堀場製作所製EMAX-7000）を用いたマッピング分析によりシリコン元素及びアルミニウム元素の分析を行い、その後、分析結果の画像処理を行ってMg2Si晶出物の面積率を算出した。測定されたアルミ基材試験片のある領域におけるMg2Si晶出物の面積率は３２%であった。
結果を表１に示す。なお、測定場所を変えてもほとんど変わりがなかった。測定された反射電子像及び分析結果の画像をそれぞれ図１、図２に示す。
2. Surface observation of cast aluminum alloy substrate The surface of the obtained aluminum substrate test piece was analyzed for silicon and aluminum elements by mapping analysis using an energy dispersive X-ray analyzer (EMAX-7000 manufactured by Horiba, Ltd.). Then, the image processing of the analysis result was performed, and the area ratio of the Mg 2 Si crystallized product was calculated. The measured area ratio of Mg 2 Si crystallized material in a certain region of the aluminum base specimen was 32%.
The results are shown in Table 1. Note that there was almost no change even when the measurement location was changed. The measured backscattered electron image and the analysis result image are shown in FIGS. 1 and 2, respectively.
３．アルミ鋳造合金部材の調製
続いて、得られたアルミ基材試験片について、30wt%-硝酸水溶液に常温で１分間浸漬した後にイオン交換水で十分に水洗し、次いで5wt%-水酸化ナトリウム溶液に５０℃で１分間浸漬した後に水洗し、更に、30wt%-硝酸水溶液に常温で１分間浸漬した後に水洗する前処理を施した。
3. Preparation of Aluminum Cast Alloy Member Next, the obtained aluminum base specimen was immersed in a 30 wt% -nitric acid aqueous solution at room temperature for 1 minute, then thoroughly washed with ion-exchanged water, and then into a 5 wt% -sodium hydroxide solution. The sample was immersed in water at 50 ° C. for 1 minute and then washed with water, and further pretreated by immersing in a 30 wt% nitric acid aqueous solution at room temperature for 1 minute and then washing with water.
このようにして前処理が施されたアルミ基材試験片について、10wt%-硫酸溶液中に４０℃で１０分間浸漬した後に水洗するエッチング処理を施し、次いで水洗した後に８０℃の熱風で５分間乾燥させ、表面に凹状部を有するアルミ部材試験片（実施例１のアルミ鋳造合金部材）を作製した。 The aluminum base test piece thus pretreated was subjected to an etching treatment in which it was immersed in a 10 wt% -sulfuric acid solution at 40 ° C. for 10 minutes and then washed with water, and then washed with water and then heated with hot air at 80 ° C. for 5 minutes. An aluminum member test piece (aluminum cast alloy member of Example 1) having a concave portion on the surface was produced by drying.
４．アルミ鋳造合金部材の表面観察
得られたアルミ部材試験片の表面を、走査型電子顕微鏡（日立製FE-SEM、S-4500形）を用いて観察し、その後、画像処理を行ってアルミ部材試験片の凹状部の面積率を算出した。観察されたアルミ部材試験片の表面は図３のＳＥＭ写真に示す通りであった。また、測定されたアルミ部材試験片のある領域の凹状部の面積率は６０%であった。
結果を表１に示す。なお、観察場所を変えても凹状部の面積率にほとんど変わりがなかった。ＳＥＭ写真の画像処理結果を図４に示す。
4). Surface observation of cast aluminum alloy member The surface of the obtained aluminum member test piece was observed with a scanning electron microscope (Hitachi FE-SEM, S-4500 type), and then image processing was performed to test the aluminum member. The area ratio of the concave part of the piece was calculated. The surface of the observed aluminum member test piece was as shown in the SEM photograph of FIG. Further, the area ratio of the concave portion in the region where the aluminum member test piece was measured was 60%.
The results are shown in Table 1. In addition, even if the observation place was changed, there was almost no change in the area ratio of the concave portion. The image processing result of the SEM photograph is shown in FIG.
５．アルミ鋳造合金部材の表面のSi付着量
作製したアルミ部材試験片の表面について、JIS Z 0237に準拠し、２kgのローラーを用いて２kgの荷重下に行った粘着テープ・粘着シート試験法を適用し、アルミ部材試験片の表面に存在するＳiをテープに付着させ、このテープに付着したＳiの量をＩＣＰ発光分光分析法にて定量した。結果はSi付着量が０μg/cm2であった。
結果を表１に示す。
5. The amount of Si adhesion on the surface of the aluminum cast alloy member The adhesive tape / adhesive sheet test method performed under a load of 2 kg using a 2 kg roller in accordance with JIS Z 0237 was applied to the surface of the prepared aluminum member test piece. Then, Si present on the surface of the aluminum member test piece was attached to the tape, and the amount of Si attached to the tape was quantified by ICP emission spectrometry. As a result, the Si adhesion amount was 0 μg / cm 2 .
The results are shown in Table 1.
６．せん断破壊荷重測定試験
以上のようにして得られた実施例１のアルミ部材試験片を射出成形機（NISSEI社製ST10R2V）の金型内にセットし、熱可塑性樹脂として充填剤含有ポリフェニレンスルフィド樹脂（ポリプラスチックス社製PPS グレード名1140A6）を用い、射出時間（保圧時間を含む）５秒、射出速度６０mm/秒、保圧力９０MPa、成形温度３１０℃、及び金型温度１８０℃の成形条件で射出成形し、図１２に示すように、４０mm×４０mm×３mmの大きさのアルミ部材試験片１の表面に、大きさ４０mm×１０mm×５mmの樹脂成形体２を１０mm×５mmの接合面積で接合させ、上記アルミ部材試験片１の表面の一部に樹脂成形体２が一体的に固着したせん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製した。
6). Shear fracture load measurement test The aluminum member test piece of Example 1 obtained as described above was set in a mold of an injection molding machine (ST10R2V manufactured by NISSEI), and a polyphenylene sulfide resin containing a filler as a thermoplastic resin ( Polyplastics PPS grade name 1140A6), injection time (including holding time) 5 seconds, injection speed 60mm / second, holding pressure 90MPa, molding temperature 310 ℃, mold temperature 180 ℃ As shown in FIG. 12, the resin molded body 2 having a size of 40 mm × 10 mm × 5 mm is bonded to the surface of the aluminum member test piece 1 having a size of 40 mm × 40 mm × 3 mm with a bonding area of 10 mm × 5 mm. Thus, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test in which the resin molded body 2 was integrally fixed to a part of the surface of the aluminum member test piece 1 was produced.
次に、せん断強度測定試験機（島津製作所製：100kNオートグラフ）を用い、図１３に示すように、その試験片固定用治具３に上記のせん断破壊加重測定試験用のアルミ樹脂試験片を図示外のボルトで固定し、接合部から０．１mm離れた位置で樹脂成形体２上に押しジグ４を当て、この押しジグ４により樹脂成形体２にせん断荷重を加え、アルミ部材試験片１と樹脂成形体２との間の接合部の剥離状態を調べた。この時の剥離形態について、樹脂成形体２の樹脂がアルミ部材試験片１側に接合面積の７０%以上の割合で残る「凝集破壊」である場合を最良好（◎）とし、また、樹脂がアルミ部材試験片１側に一部でも残る「凝集破壊」である場合を良好（○）とし、更に、樹脂がアルミ部材試験片１側に残らずに剥離が接合界面で発生した場合を不良（×）として評価した。結果は最良好（◎）であった。
結果を表１に示す。
Next, using a shear strength measurement tester (manufactured by Shimadzu Corporation: 100 kN autograph), as shown in FIG. 13, the above-mentioned shear fracture load measurement test aluminum resin test piece is placed on the test piece fixing jig 3. Fixing with a bolt (not shown), a pressing jig 4 is applied on the resin molded body 2 at a position 0.1 mm away from the joint, and a shear load is applied to the resin molded body 2 by the pressing jig 4 to test the aluminum member test piece 1. The peeled state of the joint between the resin molded body 2 and the resin molded body 2 was examined. As for the peeling form at this time, the case where the resin of the resin molded body 2 is “cohesive failure” remaining at a ratio of 70% or more of the bonding area on the aluminum member test piece 1 side is the best (（). A case where “cohesive failure” remains even on the aluminum member test piece 1 side is judged as good (◯), and a case where the resin does not remain on the aluminum member test piece 1 side and peeling occurs at the joining interface is defective ( X). The result was the best (◎).
The results are shown in Table 1.
〔実施例２〕
Ｓi：９．５質量%、Ｆe：０．０１質量%、Ｃu：０．０８質量%、Ｍn：０．１０質量%、Ｍg：１．９５質量%、Ｎi：０．０１質量%を含むアルミ合金溶湯のダイカスト鋳込みを行い、鋳造時の冷却速度を９０℃/秒とした以外は、実施例１と同様にして実施例２のアルミ基材試験片（アルミ鋳造合金基材）を作製し、実施例１と同様にしてその表面におけるMg2Si晶出物の面積率を求めた。
結果は、Mg2Si晶出物の面積率が２１%であり、測定場所を変えてもほとんど変わりがなかった。結果を表１に示す。
[Example 2]
Aluminum containing Si: 9.5% by mass, Fe: 0.01% by mass, Cu: 0.08% by mass, Mn: 0.10% by mass, Mg: 1.95% by mass, Ni: 0.01% by mass An aluminum substrate test piece (aluminum cast alloy substrate) of Example 2 was produced in the same manner as in Example 1 except that die casting of the molten alloy was performed and the cooling rate during casting was set to 90 ° C./second. In the same manner as in Example 1, the area ratio of Mg 2 Si crystallized matter on the surface was determined.
As a result, the area ratio of the Mg 2 Si crystallized product was 21%, and there was almost no change even when the measurement location was changed. The results are shown in Table 1.
次に、実施例２のアルミ基材試験片について、実施例１と同様にして前処理を施した後、１０wt%硫酸溶液中に４０℃で１０分間浸漬した後に水洗するエッチング処理を施した後に水洗し、８０℃の熱風で５分間乾燥させ、実施例２のアルミ部材試験片（アルミ鋳造合金部材）を作製し、実施例１と同様にして、その表面における凹状部の面積率とSi付着量とを求めた。
観察されたアルミ部材試験片の表面は図５のＳＥＭ写真に示す通りであり、算出された凹状部の面積率は４２%であって、観察場所を変えてもほとんど変わりがなく、また、Si付着量が０μg/cm2であった。
Next, the aluminum substrate test piece of Example 2 was pretreated in the same manner as in Example 1, and then subjected to an etching treatment of immersing in a 10 wt% sulfuric acid solution at 40 ° C. for 10 minutes and then washing with water. Washed with water and dried with hot air of 80 ° C. for 5 minutes to produce an aluminum member test piece (aluminum cast alloy member) of Example 2, and in the same manner as in Example 1, the area ratio of the concave portion on the surface and Si adhesion We asked for quantity.
The surface of the observed aluminum member test piece is as shown in the SEM photograph of FIG. 5, and the calculated area ratio of the concave portion is 42%, and there is almost no change even if the observation place is changed. The amount of adhesion was 0 μg / cm 2 .
続いて、上記実施例１と同様にして、せん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製し、上記アルミ樹脂試験片のせん断強度を測定し、評価した。
結果を、実施例１の結果と共に、表１に示す。
Subsequently, in the same manner as in Example 1, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test was prepared, and the shear strength of the aluminum resin test piece was measured and evaluated.
The results are shown in Table 1 together with the results of Example 1.
〔実施例３〕
Ｓi：０．９９質量%、Ｆe：０．０１質量%、Ｃu：０．０１質量%、Ｍn：１．１０質量%、Ｍg：３．６０質量%、Ｎi：０．０１質量%を含むアルミ合金溶湯のダイカスト鋳込みを行い、鋳造時の冷却速度を９０℃/秒とした以外は、実施例１と同様にして実施例３のアルミ基材試験片（アルミ鋳造合金基材）を作製し、実施例１と同様にしてその表面におけるMg2Si晶出物の面積率を求めた。
結果は、Mg2Si晶出物の面積率が２０%であり、測定場所を変えてもほとんど変わりがなかった。結果を表１に示す。
Example 3
Aluminum containing Si: 0.99 mass%, Fe: 0.01 mass%, Cu: 0.01 mass%, Mn: 1.10 mass%, Mg: 3.60 mass%, Ni: 0.01 mass% An aluminum substrate test piece (aluminum cast alloy substrate) of Example 3 was prepared in the same manner as in Example 1 except that die casting of the molten alloy was performed and the cooling rate during casting was set to 90 ° C./second. In the same manner as in Example 1, the area ratio of Mg 2 Si crystallized matter on the surface was determined.
As a result, the area ratio of the Mg 2 Si crystallized product was 20%, and there was almost no change even when the measurement location was changed. The results are shown in Table 1.
次に、実施例３のアルミ基材試験片について、実施例１と同様にして前処理を施した後、１０wt%硫酸溶液中に４０℃で１０分間浸漬した後に水洗するエッチング処理を施した後に水洗し、８０℃の熱風で５分間乾燥させ、実施例３のアルミ部材試験片（アルミ鋳造合金部材）を作製し、実施例１と同様にして、その表面における凹状部の面積率とSi付着量とを求めた。
観察されたアルミ部材試験片の表面は図６のＳＥＭ写真に示す通りであり、算出された凹状部の面積率は４３%であって、観察場所を変えてもほとんど変わりがなく、また、Si付着量が０μg/cm2であった。
Next, the aluminum substrate test piece of Example 3 was pretreated in the same manner as in Example 1, and then subjected to an etching treatment of immersing in a 10 wt% sulfuric acid solution at 40 ° C. for 10 minutes and then washing with water. Washed with water and dried with hot air at 80 ° C. for 5 minutes to prepare an aluminum member test piece (aluminum cast alloy member) of Example 3, and in the same manner as in Example 1, the area ratio of the concave portion on the surface and Si adhesion We asked for quantity.
The surface of the observed aluminum member test piece is as shown in the SEM photograph of FIG. 6, and the calculated area ratio of the concave portion is 43%, and there is almost no change even if the observation place is changed. The amount of adhesion was 0 μg / cm 2 .
続いて、上記実施例１と同様にして、せん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製し、上記アルミ樹脂試験片のせん断強度を測定し、評価した。
結果を、実施例１の結果と共に、表１に示す。
Subsequently, in the same manner as in Example 1, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test was prepared, and the shear strength of the aluminum resin test piece was measured and evaluated.
The results are shown in Table 1 together with the results of Example 1.
〔実施例４〕
Ｓi：１３．０１質量%、Ｆe：０．０１質量%、Ｃu：０．０１質量%、Ｍn：１．１０質量%、Ｍg：１．９９質量%、Ｎi：０．０１質量%を含むアルミ合金溶湯のダイカスト鋳込みを行い、鋳造時の冷却速度を９０℃/秒とした以外は、実施例１と同様にして実施例４のアルミ基材試験片（アルミ鋳造合金基材）を作製し、実施例１と同様にしてその表面におけるMg2Si晶出物の面積率を求めた。
結果は、Mg2Si晶出物の面積率が２２%であり、測定場所を変えてもほとんど変わりがなかった。結果を表１に示す。
Example 4
Si: Aluminum containing 13.01% by mass, Fe: 0.01% by mass, Cu: 0.01% by mass, Mn: 1.10% by mass, Mg: 1.99% by mass, Ni: 0.01% by mass An aluminum substrate test piece (aluminum cast alloy substrate) of Example 4 was produced in the same manner as in Example 1 except that die casting of the molten alloy was performed and the cooling rate during casting was 90 ° C./second, In the same manner as in Example 1, the area ratio of Mg 2 Si crystallized matter on the surface was determined.
As a result, the area ratio of the Mg 2 Si crystallized product was 22%, and there was almost no change even when the measurement location was changed. The results are shown in Table 1.
次に、実施例４のアルミ基材試験片について、実施例１と同様にして前処理を施した後、１０wt%硫酸溶液中に４０℃で１０分間浸漬した後に水洗するエッチング処理を施した後に水洗し、８０℃の熱風で５分間乾燥させ、実施例４のアルミ部材試験片（アルミ鋳造合金部材）を作製し、実施例１と同様にして、その表面における凹状部の面積率とSi付着量とを求めた。
観察されたアルミ部材試験片の表面は図７のＳＥＭ写真に示す通りであり、算出された凹状部の面積率は５１%であって、観察場所を変えてもほとんど変わりがなく、また、Si付着量が０μg/cm2であった。
Next, the aluminum substrate test piece of Example 4 was pretreated in the same manner as in Example 1, and after being immersed in a 10 wt% sulfuric acid solution at 40 ° C. for 10 minutes and then washed with water. Washed with water and dried with hot air at 80 ° C. for 5 minutes to produce an aluminum member test piece (aluminum cast alloy member) of Example 4, and in the same manner as in Example 1, the area ratio of the concave portion on the surface and Si adhesion We asked for quantity.
The observed surface of the aluminum member test piece is as shown in the SEM photograph of FIG. 7, and the calculated area ratio of the concave portion is 51%, and there is almost no change even if the observation place is changed. The amount of adhesion was 0 μg / cm 2 .
続いて、上記実施例１と同様にして、せん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製し、上記アルミ樹脂試験片のせん断強度を測定し、評価した。
結果を、実施例１の結果と共に、表１に示す。
Subsequently, in the same manner as in Example 1, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test was prepared, and the shear strength of the aluminum resin test piece was measured and evaluated.
The results are shown in Table 1 together with the results of Example 1.
〔実施例５〕
Ｓi：３．０１質量%、Ｆe：０．０１質量%、Ｃu：０．０１質量%、Ｍn：１．１０質量%、Ｍg：５．９９質量%、Ｎi：０．０１質量%を含むアルミ合金溶湯のダイカスト鋳込みを行い、鋳造時の冷却速度を９０℃/秒とした以外は、実施例１と同様にしてアルミ鋳造合金材を作製し、このアルミ鋳造合金材について処理温度５４０℃及び処理時間３時間の条件で溶体化処理を行い、その後すみやかに水中で焼き入れを行った後に処理温度２００℃及び３時間の条件で時効処理を実施し、得られた時効処理後のアルミ鋳造合金材から実施例１と同じ大きさの実施例５のアルミ基材試験片（アルミ鋳造合金基材）を切り出して作製し、実施例１と同様にしてその表面におけるMg2Si晶出物の面積率を求めた。
結果は、Mg2Si晶出物の面積率が３０%であり、測定場所を変えてもほとんど変わりがなかった。結果を表１に示す。
Example 5
Aluminum containing Si: 3.01% by mass, Fe: 0.01% by mass, Cu: 0.01% by mass, Mn: 1.10% by mass, Mg: 5.99% by mass, Ni: 0.01% by mass An aluminum cast alloy material was produced in the same manner as in Example 1 except that the molten alloy was die-cast and the cooling rate during casting was 90 ° C./sec. The aluminum cast alloy material was treated at a processing temperature of 540 ° C. Solution treatment is performed for 3 hours, and after quenching in water immediately, aging treatment is performed at a treatment temperature of 200 ° C. for 3 hours, and the resulting aluminum casting alloy material after aging treatment is obtained. An aluminum substrate test piece (aluminum cast alloy substrate) of Example 5 having the same size as that of Example 1 was cut out and produced, and the area ratio of Mg 2 Si crystallized material on the surface in the same manner as in Example 1 Asked.
As a result, the area ratio of the Mg 2 Si crystallized product was 30%, and there was almost no change even when the measurement location was changed. The results are shown in Table 1.
次に、実施例５のアルミ基材試験片について、実施例１と同様にして前処理を施した後、１０wt%硫酸溶液中に８０℃で５分間浸漬した後に水洗するエッチング処理を施した後に水洗し、８０℃の熱風で５分間乾燥させ、実施例５のアルミ部材試験片（アルミ鋳造合金部材）を作製し、実施例１と同様にして、その表面における凹状部の面積率とSi付着量とを求めた。
観察されたアルミ部材試験片の表面は図８のＳＥＭ写真に示す通りであり、算出された凹状部の面積率は５５%であって、観察場所を変えてもほとんど変わりがなく、また、Si付着量が０μg/cm2であった。
Next, the aluminum substrate test piece of Example 5 was pretreated in the same manner as in Example 1, and then subjected to an etching treatment of immersing in a 10 wt% sulfuric acid solution at 80 ° C. for 5 minutes and then washing with water. Washed with water and dried with hot air at 80 ° C. for 5 minutes to produce an aluminum member test piece (aluminum cast alloy member) of Example 5, and in the same manner as in Example 1, the area ratio of the concave portion on the surface and Si adhesion We asked for quantity.
The surface of the observed aluminum member test piece is as shown in the SEM photograph of FIG. 8, and the calculated area ratio of the concave portion is 55%, and there is almost no change even if the observation place is changed. The amount of adhesion was 0 μg / cm 2 .
続いて、上記実施例１と同様にして、せん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製し、上記アルミ樹脂試験片のせん断強度を測定し、評価した。
結果を、実施例１の結果と共に、表１に示す。
Subsequently, in the same manner as in Example 1, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test was prepared, and the shear strength of the aluminum resin test piece was measured and evaluated.
The results are shown in Table 1 together with the results of Example 1.
〔実施例６〕
Ｓi：３．０１質量%、Ｆe：０．０１質量%、Ｃu：０．０１質量%、Ｍn：１．１０質量%、Ｍg：５．９９質量%、Ｎi：０．０１質量%を含むアルミ合金溶湯のダイカスト鋳込みを行い、鋳造時の冷却速度を９０℃/秒とした以外は、実施例１と同様にしてアルミ鋳造合金材を作製し、このアルミ鋳造合金材について処理温度５４０℃及び処理時間３時間の条件で溶体化処理を行い、その後すみやかに水中で焼き入れを行った後に処理温度３００℃及び３時間の条件で時効処理を実施し、得られた時効処理後のアルミ鋳造合金材から実施例１と同じ大きさの実施例６のアルミ基材試験片（アルミ鋳造合金基材）を切り出して作製し、実施例１と同様にしてその表面におけるMg2Si晶出物の面積率を求めた。
結果は、Mg2Si晶出物の面積率が３４%であり、測定場所を変えてもほとんど変わりがなかった。結果を表１に示す。
Example 6
Aluminum containing Si: 3.01% by mass, Fe: 0.01% by mass, Cu: 0.01% by mass, Mn: 1.10% by mass, Mg: 5.99% by mass, Ni: 0.01% by mass An aluminum cast alloy material was produced in the same manner as in Example 1 except that the molten alloy was die-cast and the cooling rate during casting was 90 ° C./sec. The aluminum cast alloy material was treated at a processing temperature of 540 ° C. The aluminum casting alloy material after the aging treatment was obtained after solution treatment was performed for 3 hours, followed by rapid quenching in water followed by aging treatment at 300 ° C for 3 hours. An aluminum substrate test piece (aluminum cast alloy substrate) of Example 6 having the same size as that of Example 1 was cut out and produced, and the area ratio of Mg 2 Si crystallized material on the surface in the same manner as in Example 1 Asked.
As a result, the area ratio of the Mg 2 Si crystallized product was 34%, and there was almost no change even when the measurement location was changed. The results are shown in Table 1.
次に、実施例６のアルミ基材試験片について、実施例１と同様にして前処理を施した後、１０wt%硫酸溶液中に４０℃で１０分間浸漬した後に水洗するエッチング処理を施した後に水洗し、８０℃の熱風で５分間乾燥させ、実施例６のアルミ部材試験片（アルミ鋳造合金部材）を作製し、実施例１と同様にして、その表面における凹状部の面積率とSi付着量とを求めた。
観察されたアルミ部材試験片の表面は図９のＳＥＭ写真に示す通りであり、算出された凹状部の面積率は７０%であって、観察場所を変えてもほとんど変わりがなく、また、Si付着量が０μg/cm2であった。
Next, the aluminum substrate test piece of Example 6 was pretreated in the same manner as in Example 1, and then subjected to an etching treatment in which it was immersed in a 10 wt% sulfuric acid solution at 40 ° C. for 10 minutes and then washed with water. Washed with water and dried with hot air at 80 ° C. for 5 minutes to produce an aluminum member test piece (aluminum cast alloy member) of Example 6, and in the same manner as in Example 1, the area ratio of the concave portion on the surface and Si adhesion We asked for quantity.
The surface of the observed aluminum member test piece is as shown in the SEM photograph of FIG. 9, and the calculated area ratio of the concave portion is 70%, and there is almost no change even if the observation place is changed. The amount of adhesion was 0 μg / cm 2 .
続いて、上記実施例１と同様にして、せん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製し、上記アルミ樹脂試験片のせん断強度を測定し、評価した。
結果を、実施例１の結果と共に、表１に示す。
Subsequently, in the same manner as in Example 1, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test was prepared, and the shear strength of the aluminum resin test piece was measured and evaluated.
The results are shown in Table 1 together with the results of Example 1.
〔比較例１〕
Ｓi：１１．０３質量%、Ｆe：０．８質量%、Ｃu：３．０７質量%、Ｍn：０．２２質量%、Ｍg：０．２７質量%、Ｎi：０．０９質量%を含むアルミ合金溶湯のダイカスト鋳込みを行い、鋳造時の冷却速度を９０℃/秒とした以外は、実施例１と同様にして比較例１のアルミ基材試験片（アルミ鋳造合金基材）を作製し、実施例１と同様にしてその表面におけるMg2Si晶出物の面積率を求めた。
結果は、Mg2Si晶出物の面積率が２%であり、測定場所を変えてもほとんど変わりがなかった。結果を表１に示す。
[Comparative Example 1]
Aluminum containing Si: 11.03 mass%, Fe: 0.8 mass%, Cu: 3.07 mass%, Mn: 0.22 mass%, Mg: 0.27 mass%, Ni: 0.09 mass% An aluminum substrate test piece (aluminum cast alloy substrate) of Comparative Example 1 was prepared in the same manner as in Example 1 except that die casting of the molten alloy was performed and the cooling rate during casting was 90 ° C./second, In the same manner as in Example 1, the area ratio of Mg 2 Si crystallized matter on the surface was determined.
As a result, the area ratio of the Mg 2 Si crystallized product was 2%, and there was almost no change even when the measurement location was changed. The results are shown in Table 1.
次に、比較例１のアルミ基材試験片について、実施例１と同様にして前処理を施した後、１０wt%硫酸溶液中に４０℃で１０分間浸漬した後に水洗するエッチング処理を施した後に水洗し、８０℃の熱風で５分間乾燥させ、比較例１のアルミ部材試験片（アルミ鋳造合金部材）を作製し、実施例１と同様にして、その表面における凹状部の面積率とSi付着量とを求めた。
観察されたアルミ部材試験片の表面は図１０のＳＥＭ写真に示す通りであり、算出された凹状部の面積率は５%であって、観察場所を変えてもほとんど変わりがなく、また、Si付着量が０μg/cm2であった。
Next, after pre-treating the aluminum substrate test piece of Comparative Example 1 in the same manner as in Example 1, it was immersed in a 10 wt% sulfuric acid solution at 40 ° C. for 10 minutes and then subjected to an etching treatment for washing with water. Washed with water and dried with hot air of 80 ° C. for 5 minutes to produce an aluminum member test piece (aluminum cast alloy member) of Comparative Example 1, and in the same manner as in Example 1, the area ratio of the concave portion on the surface and Si adhesion We asked for quantity.
The surface of the observed aluminum member test piece is as shown in the SEM photograph of FIG. 10, and the calculated area ratio of the concave portion is 5%, and there is almost no change even if the observation place is changed. The amount of adhesion was 0 μg / cm 2 .
続いて、上記実施例１と同様にして、せん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製し、上記アルミ樹脂試験片のせん断強度を測定し、評価した。
結果を、実施例１の結果と共に、表１に示す。
Subsequently, in the same manner as in Example 1, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test was prepared, and the shear strength of the aluminum resin test piece was measured and evaluated.
The results are shown in Table 1 together with the results of Example 1.
〔比較例２〕
Ｓi：３．３質量%、Ｆe：０．４質量%、Ｃu：０．０２質量%、Ｍn：０．４質量%、Ｍg：６．０質量%、Ｎi：０．０２質量%を含むアルミ合金溶湯のダイカスト鋳込みを行った以外は、実施例１と同様にして比較例２のアルミ基材試験片（アルミ鋳造合金基材）を作製し、実施例１と同様にしてその表面におけるMg2Si晶出物の面積率を求めた。
結果は、Mg2Si晶出物の面積率が３２%であり、測定場所を変えてもほとんど変わりがなかった。結果を表１に示す。
[Comparative Example 2]
Aluminum containing Si: 3.3% by mass, Fe: 0.4% by mass, Cu: 0.02% by mass, Mn: 0.4% by mass, Mg: 6.0% by mass, Ni: 0.02% by mass An aluminum substrate test piece (aluminum cast alloy substrate) of Comparative Example 2 was prepared in the same manner as in Example 1 except that the molten alloy was die cast, and Mg 2 on the surface thereof was prepared in the same manner as in Example 1. The area ratio of the Si crystallized product was determined.
As a result, the area ratio of the Mg 2 Si crystallized product was 32%, and there was almost no change even when the measurement location was changed. The results are shown in Table 1.
次に、比較例２のアルミ基材試験片について、実施例１と同様にして前処理を施した後、１０wt%硫酸溶液中に４０℃で６０分間浸漬した後に水洗するエッチング処理を施した後に水洗し、８０℃の熱風で５分間乾燥させ、比較例２のアルミ部材試験片（アルミ鋳造合金部材）を作製し、実施例１と同様にして、その表面における凹状部の面積率とSi付着量とを求めた。
観察されたアルミ部材試験片の表面は図１１のＳＥＭ写真に示す通りであり、算出された凹状部の面積率は７０%であって、観察場所を変えてもほとんど変わりがなく、また、Si付着量が１００μg/cm2であった。
Next, the aluminum substrate test piece of Comparative Example 2 was pretreated in the same manner as in Example 1, and then subjected to an etching treatment of immersing in a 10 wt% sulfuric acid solution at 40 ° C. for 60 minutes and then washing with water. Washed with water and dried with hot air at 80 ° C. for 5 minutes to produce an aluminum member test piece (aluminum cast alloy member) of Comparative Example 2, and in the same manner as in Example 1, the area ratio of the concave portion on the surface and Si adhesion We asked for quantity.
The surface of the observed aluminum member test piece is as shown in the SEM photograph of FIG. 11, and the calculated area ratio of the concave portion is 70%, and there is almost no change even if the observation place is changed. The adhesion amount was 100 μg / cm 2 .
続いて、上記実施例１と同様にして、せん断強度測定試験用のアルミ樹脂試験片（アルミ−樹脂複合体）を作製し、上記アルミ樹脂試験片のせん断強度を測定し、評価した。
結果を、実施例１の結果と共に、表１に示す。
Subsequently, in the same manner as in Example 1, an aluminum resin test piece (aluminum-resin composite) for a shear strength measurement test was prepared, and the shear strength of the aluminum resin test piece was measured and evaluated.
The results are shown in Table 1 together with the results of Example 1.
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| JP2017538031A (en) * | 2014-10-29 | 2017-12-21 | ケーエムダブリュ・インコーポレーテッド | Die-casting aluminum alloy with improved corrosion resistance, frequency filter, and method for manufacturing communication device parts |
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| JP2020199740A (en) * | 2019-06-13 | 2020-12-17 | 株式会社ショーワ | Manufacturing method of bonded body |
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